Multi-layer absorbent wound dressing

ABSTRACT

A multi-layer wound dressing comprising at least two absorbent layers, and materials for forming absorbent layers are provided. The absorbent layers have different absorbencies, with the layer closest to the wound having a lower absorbency than the layer furthest from the wound. The wound dressing typically contains additional non-absorbing layers, such as a backing film and wound-facing film. The dressing provides absorbency of wound exudates while preventing the absorbent material from entering the wound. In specific implementations the dressing is substantially transparent prior to application to a wound, as well as after application to the wound when body fluids have been absorbed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. patent application Ser. No.09/657,486, filed Sep. 8, 2000, now U.S. Pat. No. 6,903,243.

FIELD OF THE INVENTION

The present invention is directed to novel body fluid absorbingmaterials; and to absorbent articles used as wound dressings, includingmulti-layer absorbent articles having at least two absorbent layers.

BACKGROUND OF THE INVENTION

Proper wound dressings are an essential medical supply for treatinginjuries. Without dressings, the wound exudate accumulates and createsbreeding grounds for harmful microorganisms. Each year, sterile wounddressings are applied to millions of wounds in order to absorb woundexudate while promoting sterility.

Traditional wound dressings have included various cloth and fibermaterials as exudates absorbents, such as cotton pads. Unfortunately,these traditional dressings provide relatively limited absorbency andmust be changed frequently. Their ability to preserve sterility is alsolimited, and scabs that form as the wounds heal tend to stick to thedressings. After the dressings are removed, these scabs are alsoremoved, which can be painful and interfere with healing.

Efforts have been made to improve upon these traditional wound dressingsby applying a non-stick perforated film to the wound-facing side of thedressing. These non-stick films are designed to allow wound exudate topenetrate to the absorbent, while restricting the physical contactbetween the absorbent and wound in an effort to reduce undesirableadherence between the two. However, these perforated films do nothing toimprove on the absorbency of traditional absorbent materials used indressings.

In order to improve upon absorbency, various alternative absorbentmaterials have been developed. For example, hydrophilic hydrocolloidsand hydrogels have been created that provide a translucent ortransparent absorbent layer. Such dressings can allow for generalinspection of the healing wound. Unfortunately, some such dressings havethe problem that the absorbent deforms and partially disintegrates uponswelling. Specifically, as the absorbent takes in fluid, it often bendsand buckles such that some of the absorbent material breaks away fromthe dressing and enters the wound. This absorbent material can be leftin the wound upon removal of the dressing, which is undesirable forcosmetic and therapeutic reasons. In addition, such materials often haverelatively high moisture content prior to application, which can limittheir ability to absorb additional water after they are applied.

Therefore, a need exists for a wound dressing that improves on existingdressing materials and technology.

SUMMARY OF THE INVENTION

The present invention is directed to multi-layer wound dressings. Themulti-layer wound dressings allow for high absorbency of body fluidswhile providing good durability and minimal degradation during use. Inaddition, in specific implementations, the multi-layer wound dressingsare transparent and remain transparent when wet; and the dressings canbe cut by clinicians to conform to the shape and size of the wound beingcovered. Also described are novel compositions useful as body fluidabsorbing materials.

The wound dressings of the invention include at least two absorbentlayers: a first absorbent layer and a second absorbent layer. The firstabsorbent layer is typically more absorbent than the second absorbentlayer, and can retain a greater volume of body fluids than the secondabsorbent layer. The second absorbent layer is positioned such that itis located between the first absorbent layer and the wound. This secondabsorbent layer provides integrity to the wound dressing and avoidstransfer of the first absorbent layer into the wound.

The first absorbent layer typically contains the reaction product of ahydrophilic, ethylenically unsaturated monomer. In one implementation,the first absorbent layer includes the reaction product of ahydrophilic, ethylenically unsaturated monomer; an acrylic acid ester ofa non-tertiary alcohol having 4 to 14 carbon atoms; and a polar,ethylenically unsaturated monomer. Specifically, the first absorbentlayer can contain the reaction product of about 50 to 80 parts by weightof the hydrophilic, ethylenically unsaturated monomer; about 5 to 30parts by weight of the acrylic acid ester of the non-tertiary alcoholhaving from 4 to 14 carbon atoms; and about 10 to 40 parts by weight ofthe polar, ethylenically unsaturated monomer. The polar, ethylenicallyunsaturated monomer comprises N-vinyl acetamide or partially neutralizedacrylic acid in specific implementations. Unless otherwise noted, it isassumed for invention compositions (including absorbent layers and bodyfluid absorbing materials) comprising the reaction product of variousparts by weight of specific monomers that the total monomer compositionis 100 parts.

The second absorbent layer is typically positioned in contact with thefirst absorbent layer and is typically less absorbent of body fluidsthan the first absorbent layer. The second absorbent layer can alsocontain the reaction product of an acrylic acid ester of a non-tertiaryalcohol having from 4 to 14 carbon atoms; a hydrophilic, ethylenicallyunsaturated monomer; and a polar, ethylenically unsaturated monomer. Inparticular implementations, the second absorbent layer contains thereaction product of about 45 to 80 parts by weight of the acrylic acidester of a non-tertiary alcohol having from 4 to 14 carbon atoms; about25 to 40 parts by weight of the hydrophilic, ethylenically unsaturatedmonomer; and about 2 to 20 parts by weight of the polar, ethylenicallyunsaturated monomer.

The first and second layers are usually formed such that they are incontact with one another across a large surface area. In particularimplementations, the absorbent layers are formed by a simultaneouspolymerization reaction. In such implementations, the unpolymerizedmonomer can be deposited simultaneously or sequentially and then curedtogether. Such simultaneously cured absorbent materials often showenhanced physical integrity because they form a strong interface. It isbelieved that such strength may be a result of some slight interfacialmixing of the layers prior to and during curing.

The second absorbent layer functions as a “barrier” between the firstabsorbent layer (which may partially “disintegrate” when exudate isabsorbed under some conditions) and the wound. Preferably the secondabsorbent layer has adhesive properties (or is a pressure sensitiveadhesive) and functions to enhance the overall integrity of the wounddressing. In this regard, the second absorbent layer ties the firstabsorbent layer to a wound-facing layer (or to the wound itself). Byhaving adhesive properties, this second absorbent layer not only aids incontrolling the absorption of exudate, but also physically joins toother components of the dressing.

As stated above, the first absorbent layer is typically significantlymore absorbent than the second absorbent layer, and preferably has anabsorbency at least 100 percent greater than the absorbency of thesecond absorbent layer. The first absorbent layer preferably absorbs atleast 400 percent of its weight after immersion in an isotonic salinesolution after 24 hours at room temperature. The second absorbent layernormally has an absorbency of at least about 50 percent by weight ofisotonic saline solution after 24 hours. Unless otherwise stated, theterm “absorbency” in the present application refers to the percent byweight of isotonic saline solution absorbed by a material testedaccording to the Saline Absorbency Method described herein.

Additional layers, such as backing layers, wound-facing layers, andadhesives are also suitable for use in certain implementations of theinvention. The invention is also directed to methods of makingmulti-layer wound dressings, including multi-layer wound dressings inwhich two or more layers of absorbent are simultaneously cured. Althoughdressings of the invention can include various materials, the inventionis also directed to specific absorbent compositions for use in wounddressings. These compositions include materials containing the reactionproduct of partially neutralized ethylenically unsaturated carboxylicacids and materials containing the reaction product of N-vinylacetamide.

The above summary of the present invention is not intended to describeeach disclosed embodiment of the present invention, but rather that isthe purpose of the following disclosure and claims in addition to thesummary.

BRIEF DESCRIPTION OF THE FIGURES

Other aspects and advantages of the invention will become apparent uponreading the following detailed description and upon reference to thedrawings in which:

FIG. 1A is a top view of a first wound dressing constructed inaccordance with the present invention.

FIG. 1B is a partial cross-sectional view taken along plane A-A′ of thewound dressing from FIG. 1A.

FIG. 1C is a partial cross-sectional view of a second wound dressingconstructed in accordance with the present invention.

While the invention is susceptible to various modifications andalternative forms, specifics thereof have been shown by way of examplein the drawings and will be described in detail. It should beunderstood, however, that the intention is not to limit the invention tothe particular embodiments described. On the contrary, the intention isto cover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention as defined by the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to multi-layer wound dressings thatallow for high absorbency of wound exudate. The wound dressings containabsorbent layers that demonstrate low disintegration after absorbingbody fluids such that absorbent material does not significantly enterthe wound. In addition, in specific implementations, the wound dressingsare substantially transparent before and after placement on a wound(with the exception of colored exudate, such as blood), and are formedsuch that they can be cut to custom sizes by clinicians prior toplacement on a wound.

In reference now to FIG. 1A, a top view is shown of a wound dressing 10constructed in accordance with a first implementation of the invention.Wound dressing 10 is shown adhered on the surface of a patient. Dressing10 is substantially transparent, with a portion of the wound 14 visiblethrough the top surface 16 of dressing 10. As used herein, transparencyrefers to dressings that permit viewing of material through the dressingwith sufficient clarity to perform general visual examinations.Preferably, the dressings are substantially transparent when thedressings are dry or wet with water or wound exudate. Such transparencytypically shows some optical distortion and may include loss in detailand resolution. Also, to the extent the wound exudate is colored byblood or other fluids, the transparency of the dressing is reduced.

A more detailed representation of this example embodiment is shown inFIG. 1B, which is a partial cross section of the wound dressing 10 takenalong plane A-A′ of FIG. 1A. Wound dressing 10 includes six layers: Abacking layer 20, an adhesive layer 22, a first absorbent layer 24, asecond absorbent layer 26, a porous or non-continuous wound-facing layer28; and a pressure sensitive adhesive 30. In the implementation shown,the first and second absorbent layers 24, 26 are positioned only withinthe interior of dressing 10, while the other four layers extend alongthe entire dressing 10, and thereby form a perimeter of substantiallynon-absorbent material. This perimeter can be advantageous because itprovides a border and frame for the absorbent layers.

In other implementations, such as that shown in FIG. 1C, the multiplelayers of the dressing 10 extend to the edges of the dressing and thusprovide a dressing that can conveniently be cut to size. In the dressing10 shown in FIG. 1C, the second absorbent layer 26 is substantiallyadhesive and provides a bond between the first absorbent layer 24 andthe wound-facing layer 28. Thus, the multiple layers of wound dressing10 are held together independent of any edge or frame bonds. This typeof wound dressing is particularly well suited to being cut by aclinician to conform to a custom shape because the wound dressing doesnot delaminate, or delaminates only an acceptable amount, upon exposureto wound exudate. These multi-layer wound dressings show favorableabsorption of exudate from wounds while also providing an integrateddressing that avoids significant shedding of the absorbent layers intothe wound dressing.

The two implementations shown in FIGS. 1A to 1C depict a six-layer wounddressing, but it will be appreciated that additional layers can beincorporated. In addition, in specific implementations, fewer layers canbe used. Thus, the invention is not limited to the embodiments depicted,but rather such embodiments are shown only to illustrate examples of theinvention.

The specific materials and positions of the various layers in the wounddressings of the invention will now be described in detail.

A. Absorbent Layers

The present invention features a first absorbent layer comprised of anabsorbent composition that is capable of rapidly absorbing moderate toheavy amounts of body fluids, while retaining sufficient structuralintegrity and transparency. This first absorbent layer typically is themost absorbent material of the dressing. The composition of the firstabsorbent layer typically includes the reaction product of:

(a) 0 to 30 parts by weight of an acrylic or methacrylic acid ester of anon-tertiary alcohol having from 4 to 14 carbon atoms;

(b) 30 to 100 parts by weight of a hydrophilic, ethylenicallyunsaturated monomer (more preferably 50 to 80 parts by weight); and

(c) 0 to 40 parts by weight of a polar, ethylenically unsaturatedmonomer different from the hydrophilic, ethylenically unsaturatedmonomer.

Although various acrylic and methacrylic acid esters of non-tertiaryalcohols having 4 to 14 carbon atoms can be used, alcohols havinggreater than 4 carbon atoms are preferred, and alcohols with from 8 to12 carbon atoms are particularly preferred.

Examples of suitable acrylic and methacrylic acid ester monomers includeesters prepared by reaction with alcohols, such as 1-butanol, 2-butanol,1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-hexanol,2-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol,3,5,5-trimethyl-1-hexanol, 3-heptanol, 1-octanol, 2-octanol, isooctanol,2-ethyl-1-hexanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol,nopol, and the like, as well as combinations thereof. In specificembodiments, the acrylic or methacrylic acid ester is selected from thegroup consisting of isooctyl acrylate, 2-ethyl hexyl acrylate, isodecylacrylate, lauryl acrylate, nopol acrylate, and combinations thereof. Theamount of the acrylic or methacrylic acid ester typically is less than80 parts by weight, preferably less than 50 parts by weight, morepreferably 5 to 30 parts by weight, and most preferably 10 to 25 partsby weight.

Examples of suitable hydrophilic, ethylenically unsaturated monomersinclude free radically reactive hydrophilic oligomers (a polymer havinga low number of repeating units, generally 2 to 20) and/or polymersincluding poly(alkylene oxides) (e.g., poly(ethylene oxide)), poly(vinylmethyl ether), poly(vinyl alcohol), cellulose derivatives, and mixturesthereof. Other suitable hydrophilic, ethylenically unsaturated monomersinclude macromonomers, e.g., acrylate-terminated poly(ethylene oxide),methoxy poly(ethylene oxide) acrylate, butoxy poly(ethylene oxide)acrylate, p-vinyl benzyl-terminated poly(ethylene oxide),acrylate-terminated poly(ethylene glycol), methacrylate-terminatedpoly(ethylene glycol), methoxy poly(ethylene glycol) methacrylate,butoxy poly(ethylene glycol) methacrylate, p-vinyl benzyl-terminatedpoly(ethylene glycol), poly(ethylene oxide) diacrylate, poly(ethyleneoxide) dimethacrylate, and combinations thereof.

The hydrophilic, ethylenically unsaturated monomer can be acrylate andmethacrylate esters prepared from mono-hydroxyl-terminated poly(loweralkylene oxides) such as polyethylene and polypropylene glycolscommercially available under the trade designation Carbowax from UnionCarbide Corp. in a variety of molecular weights (e.g., Carbowax 350,Carbowax 550, Carbowax 750, Carbowax 2000, and Carbowax 5000). Anexample of a preferred acrylate-terminated polyethylene glycol iscommercially available from Shin-Nakamura Chemical Co., Ltd., Japan,under the designation “NK Ester AM-90G.” The hydrophilic, ethylenicallyunsaturated monomer preferably is selected from the group consisting ofacrylate-terminated poly(alkylene oxides) and methacrylate-terminatedpoly(alkylene oxides). A preferred monomer is an acrylate-terminatedmethoxy poly(ethylene glycol) monomer. The amount of the hydrophilic,ethylenically unsaturated monomer typically is between 30 and 100 partsby weight, and more typically 50 to 80 parts by weight.

The polar, ethylenically unsaturated monomer preferably is selected fromthe group consisting of partially neutralized acrylic acid, methacrylicacid, itaconic acid, N-vinyl acetamide, N-methyl-N-vinyl acetamide,N-vinyl propionamide, trialkylaminoethyl(meth)acrylate salt such astrimethylaminoethyl acrylate chloride, N-vinyl-pyrrolidone,N-vinylcaprolactam, hydroxyethyl (meth)acrylate orN-(acryloyloxyethyl)pyrrolidine; with partially neutralized acrylic acidand N-vinyl acetamide being preferred. The amount of the polar,ethylenically unsaturated monomer preferably is between 0 and 40 partsby weight, more preferably 10 to 30 parts by weight, and most preferably15 to 25 parts by weight. An example of a preferred absorbentcomposition is one that includes the reaction product of laurylacrylate, acrylate-terminated methoxy poly(ethylene glycol), andpartially neutralized acrylic acid or N-vinyl acetamide.

The composition used to form the first absorbent layer preferably istacky after curing and capable of absorbing at least about 200%, morepreferably at least about 400%, and most preferably at least about 600%by weight isotonic saline after 24 hours while substantially retainingits structural integrity and transparency. Thus, the first absorbentlayer is highly absorbent.

Acrylic acid, methacrylic acid, and itaconic acid contain carboxylicacid group(s), which can react with a base such as sodium hydroxide. Forexample when one mole of acrylic acid reacts with one mole of sodiumhydroxide, one mole of sodium acrylate and one mole of water isproduced. In this case, the acrylic acid is neutralized or fullyneutralized. A mole of acrylic acid is partially neutralized when itreacts with less than one mole of sodium hydroxide. In general an acidis partially neutralized when one equivalent of acid reacts with lessthan an equivalent of base. When a ethylenically unsaturated carboxylicacid containing monomer is used in a composition of this invention, itis typically partially neutralized from 1 to 49%. Preferably, thecarboxylic acid containing monomer composition is 17% partiallyneutralized. Neutralization above 49% does not typically produce a clearmonomer solution without the addition of a large amount of water.

The second absorbent layer is also typically absorbent, but lessabsorbent than the first layer. The second layer may contain the samecomponents as described above for the first absorbent layer, however itpreferably consists of a higher concentration of the acrylic ormethacrylic acid ester monomer and is more tacky. The compositionpreferably includes the reaction product of:

(a) 45 to 75 parts by weight of an acrylic or methacrylic acid ester ofa non-tertiary alcohol having between 4 and 14 carbon atoms, inclusive;

(b) 25 to 40 parts by weight of a hydrophilic, ethylenically unsaturatedmonomer; and

(c) 2 to 20 parts by weight of a polar, ethylenically unsaturatedmonomer different from the hydrophilic, ethylenically unsaturatedmonomer, such as partially neutralized carboxylic acid containingmonomer; trialkylaminoethyl (meth)acrylates such as trimethylaminoethylacrylate chloride; N-vinyl amides such as N-vinyl acetamide,N-methyl-N-vinyl acetamide, and N-vinyl propionamide; N-vinyl lactamssuch as N-vinyl pyrolidinone and N-vinylcaprolactam, hydroxyethylacrylate, hydroxyethyl methacrylate, orN-(acryloyloxyethyl)pyrrolidinone; or combinations of these.

In specific implementations, the composition of the second absorbentlayer comprises 55 to 70 parts by weight of an acrylic or methacrylicacid ester of a non-tertiary alcohol having between 4 and 14 carbonatoms, inclusive; 30 to 35 parts by weight of a hydrophilic,ethylenically unsaturated monomer; and 4 to 15 parts by weight of apolar, ethylenically unsaturated monomer different from the hydrophilic,ethylenically unsaturated monomer.

The second absorbent layer preferably functions as a pressure sensitiveadhesive, and can control the rate of exudate influx into the firstabsorbent layer. In order for the second absorbent layer to function asan exudate rate-controlling membrane, the exudate absorbency of thesecond absorbent layer is typically lower than the exudate absorbency ofthe first absorbent layer. Preferably the exudate absorbency of thesecond absorbent layer is 2-fold lower than the exudate absorbency ofthe first absorbent layer. More preferably, the exudate absorbency ofthe second absorbent layer is 3-fold lower than the exudate absorbencyof the absorbent layer.

The first and second absorbent layers combine to provide favorableabsorbency and integrity. The first absorbent layer typically has thegreatest capacity for absorbing exudate, but the second absorbent layeraids in providing integrity to the first absorbent layer. Such integrityis aided depending upon the implementation, by providing a physicalbarrier, an absorption rate control layer, and/or a physicalstrengthening layer. In a first regard, the second layer serves as abarrier because it is more durable than the first layer when fullysaturated (in part because it is able to absorb less liquid). In asecond regard, the lower absorbency of the second absorbent layer helpsto regulate the rate of liquid uptake in the first layer. As such, thefirst layer can uniformly swell and show less disintegration. In a thirdregard, the second layer, particularly when it has adhesive properties,secures the portions of the dressing together, thereby adding strength.

The first absorbent layer is typically from 5 to 100 mils thick, andmore typically from 10 to 50 mils thick. In specific preferredimplementations, the first absorbent layer is 20 to 30 mils thick, andmore preferably about 25 mils thick. The second absorbent layer istypically less than 50 mils thick, and more typically from 1 to 10 milsthick. In specific implementations, the second absorbent layer is from 2to 4 mils thick, including implementations having a second absorbentlayer that is 3 mils thick.

In most embodiments, the first absorbent layer is at least as thick asthe second absorbent layer, and more typically significantly thickerthan the second absorbent layer. Thus, the first layer can be up to 50times thicker than the second layer in specific example embodiments.Generally, however, the thickness of the first layer is from 2 to 15times the thickness of the second layer, and more typically from 5 to 10times greater. In specific example embodiments, the first absorbentlayer is about 8 times the thickness of the second absorbent layer.

One or more multifunctional crosslinking monomers may be included in thepreparation of the absorbent layers. The term “multifunctional” as usedherein refers to crosslinking monomers which have two or more freeradically polymerizable, ethylenically unsaturated groups. Usefulmulti-functional crosslinking monomers include acrylic or methacrylicesters of diols, including 1,4-butanediol diacrylate, 1,4-butanedioldimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate,1,6-hexanediol dimethacrylate; acrylic or methacrylic esters of triolssuch as glycerol; and tetraols such as pentaerythritol.

Other useful multifunctional crosslinking monomers include polymericmultifunctional (meth) acrylates, e.g., alkylene glycol-type diacrylatesor dimethacrylates, such as diethylene glycol diacrylate, diethyleneglycol dimethacrylate, triethylene glycol diacrylate, diethylene glycoldimethacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol400 diacrylate, polyethylene glycol 600 diacrylate, polyethylene glycol200 dimethacrylate, polyethylene glycol 400 dimethacrylate, polyethyleneglycol 600 dimethacrylate, polyethylene glycol 1000 dimethacrylate,polypropylene glycol 400 diacrylate, polypropylene glycol 400dimethacrylate; polyvinylic crosslinking agents such as substituted andunsubstituted divinylbenzene; trimethylolpropane-type tri- andtetra-acrylates or tri-methacrylates, such as trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate, ethoxylatedtrimethylolpropane triacrylate, trimethylolpropane tetraacrylate;pentaerythritol-type tri- and tetra-acrylates or tri- andtetra-methacrylates, such as pentaerythritol triacrylate,pentaerythritol tetramethacrylate; isocyanurate-type triacrylates ortrimethacrylates, such as tris(acryloxyethyl) isocyanurate,tris(methacryloxyethyl) isocyanurate; and bisphenol A-type diacrylatesor dimethacrylates, such as ethoxylated bisphenol A diacrylate,ethoxylated bisphenol A dimethacrylate; and difunctional urethaneacrylates such as “EBECRYL” 270 and “EBECRYL” 230 (1500 weight averagemolecular weight and 5000 weight average molecular weight acrylatedurethanes, respectively-both available from Radcure Specialties), andcombinations thereof.

The polymerization reaction may be initiated using variousmethodologies, including photoinitiation, chemical initiation (such asusing peroxide), and thermoinitiation. When photoinitiation is used, theamount of photoinitiator used in the monomer mixture differs accordingto the extinction coefficient thereof, but typically ranges from about0.001 to about 5.0 parts by weight per 100 parts of total monomer,preferably from about 0.01 to about 5.0 parts by weight, and morepreferably from about 0.05 to about 0.5 parts by weight.

Useful photoinitiators include acetophenone, 1-hydroxycyclohexyl phenylketone, 2-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone,2-hydroxy-2-methyl-1-phenylpropan-1-one,1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one,4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1; substitutedalpha-ketols such as 2-methyl-2-hydroxypropiophenone; benzoinphotopolymerization initiators such as benzoin, benzoin methyl ether,benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, benzyldimethyl ketal; benzophenone photopolymerization initiators such asbenzophenone, benzoylbenzoic acid, methyl benzoylbenzoate,4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3,-dimethyl-4-methoxybenzophenone; and thioxanthonephotopolymerization initiators such as thioxathone, 2-chlorothioxathone,2-methylthioxathone, 2,4-dimethylthioxane, isopropylthioxathone,2,4-dichlorothioxathone, 2,4-diethyloxathone, and2,4-diisopropylthioxathone.

Other materials which may be added to the monomer mixture (before,during or after curing) include chain transfer agents or chain stoppingagents for controlling molecular weight (e.g., carbon tetrabromide,mercaptans, alcohols, methacrylates, vinyl compounds such asalpha-methyl styrene, or other monomers), tackifiers, perfumes,deodorants, and antioxidants. Preferably, these other materials do notinterfere with the polymerization or the function or clarity of thefinished dressing.

The absorbent layers may also contain plasticizers. Specific examples ofplasticizers suitable for use in the present invention are low molecularweight polyhydric alcohols such as ethylene glycol, diethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, glycerol,diglycerol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,3-butanediol,3-methyl-1,3,5-pentanetriol, 2-ethyl-1,2-hexandeiol, polyethyleneglycol, methoxypolyethylene glycol, polypropylene glycol,polyoxyethylene butyl ether, polyoxyethylene, polyoxypropylene,polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, andpolyoxyethylene polyoxypropylene pentaerythritol ether each having anaverage molecular weight of 1,000 or less. The plasticizers aretypically selected such that they do not significantly impairtransparency.

The absorbent layers may be prepared by photoinitiated bulkpolymerization according to the technique described in Martens et al.,U.S. Pat. No. 4,181,752. For example, the polymerizable monomers andphotoinitiator are mixed together in the absence of solvent andpartially polymerized to a viscosity in the range from about 500 toabout 50,000 centipoise to achieve a coatable syrup. The cross-linkingagent (if needed) and any other ingredients are then added to theprepolymerized syrup. Alternatively, these ingredients (with theexception of the cross-linking agent) can be added directly to themonomer mixture prior to pre-polymerization.

B. Backing Layer

A backing layer may be present in embodiments of the present invention.The backing layer is typically the layer farthest from the wound, andprovides additional strength to the dressing. Preferably the backinglayer is conformable to animal anatomical surfaces, and impermeable toliquid water.

The backing layer can be a transparent, conformable, elastomeric,moisture vapor permeable film. The backing film is preferablyimpermeable to liquid water and has a moisture vapor transmission rate(MVTR) of at least 300 g per 24 hr at 37° C. and 80% relative humidity.More preferably, the MVTR is at least 700 g per 24 hr at 37° C. and 80%relative humidity, and most preferable at least 2000 g per 24 hr at 37°C. and 80% relative humidity using the inverted cup method as describedin U.S. Pat. No. 4,595,001. Preferably, the backing will allow somemoisture to evaporate from the dressing while still maintaining a moistenvironment, will prevent the wound from drying out, and will preventbacteria and viral ingress. It is also desirable that the backing be alow friction material, such as that disclosed in U.S. Pat. No.5,643,187.

The dressing is preferably conformable to anatomical surfaces andstretches to accommodate flexion of joints and distension of skin. Afterthe dressing stretches, ideally it has elastic properties so that thedressing returns to the same size as before stretching. The backing mayhave a thickness of from 15 to 100 micrometers, preferably 20 to 80micrometers and more preferably 20 to 50 micrometers. The backing layermay further comprise a pressure sensitive adhesive layer to enhanceadhesion to the first absorbent layer.

Various materials can be used as the backing material. Specific examplesinclude papers, non-woven fabrics, natural fiber (e.g., cotton) fabrics,synthetic resin fabrics, synthetic resin films, synthetic resin foams,mesh-form or network papers, woven fabrics, and knit fabrics. Surgicaltapes, medical pressure-sensitive adhesive sheets, pressure-sensitiveadhesive dressings, constructed with the above films, foams, non-wovenfabrics, woven fabrics, or knits can also be used as a backing material.

Examples of suitable backing materials include polyurethanes such asEstane polyurethanes (available for B.F. Goodrich, Cleveland, Ohio)including, for example, Estane 58237, Estane 58245, and Estane 58309.Other suitable backing materials include elastomeric polyester such asHytrel polyester elastomer (E.I. duPont deNemours & Co., Wilmington,Del.), blends of polyurethane and polyester, and polyvinyl chloride.Thermoplastic polyether-amide block copolymers such as Pebax 2533 andPebax 3533 (available from Atochem Co.); and polyether-ester blockcopolymers may also be used.

C. Wound-Facing Layer

The wound dressing of the present invention preferably comprises aporous or non-continuous wound-facing layer to provide a fluid permeablebarrier between the wound site and the absorbent layers, but may beoptionally non-porous or continuous. The wound-facing layer allowstransport of moisture (i.e. fluid and vapor) from the wound to theabsorbent layers and can help isolate the wound from other components ofthe dressing. The wound-facing layer is preferably soft, flexible,conformable, non-irritating and non-sensitizing. A variety of polymersmay be used for the wound-facing layer, including polyurethane,polyethylene, polypropylene, polyamide or polyester materials. Further,the wound-facing layer may be in the form of moisture vapor permeablefilms, perforated films, woven-, non-woven or knit webs, or scrims. Apreferred wound-facing layer comprises a polyurethane film.

In one useful embodiment, the wound-facing layer is conformable toanimal (including human) anatomical surfaces, has a moisture vaportransmission rate of at least 300 grams per square meter per 24 hours atan 80% relative humidity differential at 40° C. (as described in Chen,U.S. Pat. No. 5,733,570), and contains perforations for passing woundexudate through the wound-facing layer. The wound-facing layer typicallydoes not pass liquid water under normal wound treatment conditionsexcept at the places in the wound-facing layer which are positivelyperforated to allow the exudate to pass into the absorbent layer. Thepreferred moisture vapor transmission rate of the wound-facing layer isat least 600 grams per square meter per 24 hours at an 80% relativehumidity differential at 40° C.

The wound-facing layer may further comprise a pressure sensitiveadhesive layer. The adhesive coated wound-facing layer should have theaforesaid MVTR. Porous or non-porous wound-facing layers such asperforated polyurethane, polyamide, polyester, polypropylene,polyethylene, polyether-amide, polyurethanes, chlorinated polyethylene,styrene/butadiene block copolymers (“Kraton” brand thermoplastic rubber,Shell Chemical Company, Houston, Tex.) and polyvinyl chloride and thosedescribed in U.S. Pat. No. 3,121,021 that are covered with a pressuresensitive adhesive that is not permeable to liquid water can be used forthe wound-facing layer. Optionally these films can be perforated.Additional porous materials include woven, knit, and non-wovensubstrates. It is also desirable that the wound-facing layer be a lowfriction material, such as that disclosed in U.S. Pat. No. 5,643,187.

It is preferred that the wound-facing layer have the above mentionedmoisture vapor or liquid permeability (1) so that maceration of the skinunder the wound dressing does not occur or is minimized, (2) so thatmoisture build-up under the wound-facing layer does not cause thewound-facing layer and, therefore, the wound dressing to be lifted offthe skin, and (3) to enhance proximation of the wound edges. Preferredwound-facing layers are thin polymeric films optionally coated withpressure sensitive adhesive which, in combination, have the abovecharacteristics.

The diameter of perforations or apertures in the wound-facing film arepreferably less than the thickness of the two absorbent layers. Morepreferably, the diameter is less than 70% of the thickness of theabsorbent layers. And still more preferably, the diameter is less than60% of the thickness of the absorbent layers.

The void area of the apertures is determined by measuring the averagediameter of the apertures and then calculating the average aperturearea. The number of apertures per unit area is also counted. Finally,the Percent Void Area is calculated by the equation:Percent Void Area=[(average void area per aperture)*(number of aperturesper unit area)*100]

It is preferable to use wound-facing film with a void area between 1 and20%, more preferably between 3 and 10%, and most preferably between 4and 8%. If the Percent Void Area is too low, the rate of fluidabsorption will be slow. If the Percent Void Area is too high, themechanical strength of the film will diminish to an unacceptable level.

D. Adhesive Layers

The wound-facing layer is normally attached to the wound site by meansof an adhesive which can be continuous or non-continuous, such aspattern coated. Adhesives which can be used with the wound dressings ofthe invention include adhesives which are applied to the skin such asthose described in U.S. Pat. No. Re. 24,906 (Ulrich), particularly acopolymer of 96% iso-octyl acrylate units and 4% acrylamide units and acopolymer of 94% iso-octyl acrylate units and 6% acrylic acid units.Other useful adhesives are those described in U.S. Pat. No. 3,389,827that comprise block copolymers having three or more polymer blockstructures having a general configuration --A--B--A-- wherein each A isa thermoplastic polymer block with a glass transition temperature aboveroom temperature (i.e., above about 20° C.) having an average molecularweight between about 5000 and 125,000, and B is a polymer block of aconjugated diene having an average molecular weight between about 15,000and 250,000. Additional examples of useful adhesives are acrylicadhesives such as iso-octyl acrylate/N-vinyl pyrrolidone copolymeradhesives and crosslinked acrylate adhesives such as for example thosedescribed in U.S. Pat. No. 4,112,213. Inclusion in the adhesive ofmedicaments is useful for enhancing wound healing and the inclusion ofantimicrobial agents such as iodine is useful for preventing infection.

The adhesive may optionally be a microsphere adhesive with low traumaproperties as described in U.S. Pat. No. 5,614,310; a fibrous adhesivewith low trauma properties as described in U.S. Pat. No. 6,171,985; orhave especially good adhesion to wet skin, such as the adhesivesdescribed in U.S. Pat. No. 6,198,016; and PCT Publication Nos. WO99/13866 and WO 99/13865.

The adhesive may be chosen to be permeable to water or wound exudate, orthe adhesive may be pattern coated on the front surface of the wounddressing (i.e. the surface in contact with the wound site, whether it isthe front surface of the facing or backing layers) so as to not impedethe flow of exudate to the absorbent layer, i.e. the adhesive may becoated non-continuously or at the periphery of the wound dressing.Alternatively the adhesive layer may be perforated as described for thefacing film to provide a fluid path for the exudate.

A release liner may be attached to the adhesive layer for ease ofhandling. Examples of release liners are liners made of or coated withpolyethylene, polypropylene and fluorocarbons and silicone coatedrelease papers or polyester films. Examples of the silicone coatedrelease papers are Polyslik S-8004, 83 pound (135.4 g/m²) bleachedsilicone release paper supplied by H. P. Smith Co., Chicago, Ill., and80 pound (130.5 g/m²) bleached two-sided silicone coated paper(2-80-BKG-157) supplied by Daubert Chemical Co., Dixon, Ill.

A pressure sensitive layer may also be optionally included between thebacking and the first absorbent layer and can be made from medical gradeadhesives and methods that are publicly known. Preferred adhesives areacrylate copolymers described in U.S. Pat. No. RE 24,906, particularly a97:3 iso-octyl acrylate:acrylamide copolymer. Also preferred is a70:15:15 isooctyl acrylate: methoxypolyethyleneoxide acrylate:acrylicacid terpolymer as described in U.S. Pat. No. 4,737,410 (Example 31) andU.S. Pat. No. 5,849,325. Other useful adhesives are described in U.S.Pat. Nos. 3,389,827; 4,112,213; 4,310,509 and 4,323,557. If the backingextends beyond the area of the absorbent layers, the backing adhesivemay also serve as a border skin contact adhesive.

The preferred embodiments for the facing and backing layers are thinconformable polymeric films. Generally the films are from 12 to 50microns in thickness, preferably from 12 to 25 microns. Conformabilityis somewhat dependent on thickness, thus the thinner the film the moreconformable the film.

E. Additional Materials

The wound dressing of the invention may also comprise a frame or filmoverlay that allows the dressing to be more easily applied to the wound.The frames are made of a relatively rigid material that maintains theshape of the dressing during handling and application to the wound site.Each frame is generally releasably adhered to the back surface of thebacking film and is removed after application of the wound dressing.Suitable frames are described in U.S. Pat. Nos. 5,531,855 and 5,738,642(Heinecke et al.).

The composition of this invention may also contain one or morepharmaceutically active agents. Examples thereof are antibacterialagents such as povidone iodine, iodine, silver, silver chloride, andchlorhexidine. Pharmaceutically active agents can be used alone or asmixtures thereof; further, medicaments can be added before the reactionproduct of this invention is cured as long as they do not interfere withpolymerization or the function or clarity of the finished dressing.Pharmacologically active agents can also be added after the reactionproduct is cured as they do not interfere with the function or clarityof the finished dressing.

F. Arrangement of Layers

Many different constructions of absorbent dressings are possible withthe wound-facing layer, the absorbent layers and the backing layer. Inone embodiment, the areas of the wound-facing layer and the backinglayer are greater than that of the absorbent layers, and thewound-facing layer is bonded to the backing layer, thereby forming apouch, with the absorbent disposed between the two. The greater area ofthe facing or backing layer forms a periphery to which an adhesive layerand a release liner may be attached.

It is preferred that the wound-facing, absorbent and backing layers ofthe present invention be at least translucent and more preferablysufficiently transparent so that the wound site to which they areapplied can be viewed through the dressing. It is advantageous to viewand evaluate the wound and healing thereof without removal of the wounddressing to avoid unnecessary handling of the wound site and exposure ofthe wound to the environment, which reduces the likelihood ofcontamination, and avoids the need to cleanse the wound as would be thecase were the dressing to be removed.

It is preferred that the dressing be both transparent and colorless sothat the color of the wound, exudate, and periwound skin may also beevaluated. Preferred transparent films for use as facing and backinglayers that allow visual inspection of the wound site includepolyurethane films, such as ESTANE™ polyurethanes (B.F. Goodrich,Cleveland, Ohio); elastomeric polyesters, such as HYTREL™ polyesterelastomers (E. I. duPont deNemours & Co., Wilmington, Del.) andpolyether block amides (PEBAX, Elf Altochem North America, Philadelphia,Pa.). Other useful films are those described in U.S. Pat. Nos.4,499,896; 4,598,004; and 5,849,325 (Heinecke et al.).

G. Methods of Making and Using Wound Dressings

The invention also features methods of treating an exuding wound thatincludes applying one of the above-described dressings to the wound andallowing the dressing to absorb body fluids exuded from the wound.Furthermore, the invention features transparent, elastomeric, bodyfluid-absorbing compositions that include the above-described reactionproducts and have the above-described properties.

In a further aspect, the invention features methods for preparing atransparent, elastomeric, body fluid-absorbing composition that includesexposing an essentially solvent-free mixture of monomers orpre-polymeric syrup to actinic radiation to form the composition. Themixture or syrup includes: (a) an acrylic or methacrylic acid ester of anon-tertiary alcohol having between 4 and 14 carbon atoms, inclusive;(b) a hydrophilic, ethylenically unsaturated monomer; and (c) a polar,ethylenically unsaturated monomer different from the hydrophilic,ethylenically unsaturated monomer. The resulting composition isessentially free of hydrocolloidal gel particles and capable ofabsorbing moderate to heavy amounts of body fluids while retaining itsstructural integrity and transparency. In preferred embodiments, themixture or syrup further includes a photoinitiator and is exposed toultraviolet radiation.

The absorbent layers of the wound dressing can be formed separately andthen adhered together either with an adhesive composition or adheredusing the inherent adhesive properties of the absorbent layers, or byincorporation of an additional adhesive between the two layers. Inanother implementation, the two layers are simultaneously curedtogether. Such simultaneous curing can be accomplished by forming layersof uncured monomer and then curing together. For example, the firstlayer of monomer can be deposited onto a surface, followed by deposit ofthe second layer of monomer, and concluded with curing of the twolayers. Alternatively, the two layers of uncured monomer can besimultaneously deposited (such as by being coextruded) and then cured.

H. EXAMPLES

This invention is further illustrated by the following examples that arenot intended to limit the scope of the invention. In the examples, allparts, ratios and percentages are by weight unless otherwise indicated.All materials are commercially available, for example from AldrichChemicals, unless otherwise indicated or described.

The following test protocols were followed in conducting theexperiments:

Saline Absorbency Method

A dry wound dressing sample (5-cm square) was weighed (W_(o)) and placedin a 180-ml bottle containing 50 ml of 0.9% Sodium Chloride Irrigation(isotonic saline solution) USP (Baxter Health Care Corp., DeerfieldIll.) at room temperature. The bottle was capped and allowed to standwithout agitation. The sample was removed at 24 hours, blotted dry, andweighed (W₂₄). The percent absorbency values were calculated using thefollowing formula and the results reported as an average of threereplications:Saline Absorbency (%)=(W ₂₄ −W _(o))×100/W _(o)Calf Bovine Serum Absorbency Method

A dry wound dressing sample (10 cm×15 cm) was applied to the upperflange of a clear polycarbonate cup, similar to a Paddington cup asdescribed in the British Pharmacopoeia, 1993, Addendum 1996, page 1943,HMSO London, England. The sample was positioned over the center of thecup cavity (3.8-cm diameter, 3-cm depth, 14-ml volume capacity) and thesample was held in place by its own pressure sensitive adhesive layer.The cup was then inverted and 12 g of calf bovine serum (Sigma-AldrichChemical Co.) was added to the cup through a port. The port was closedwith a threaded plug and the cup was placed in an incubator at 40° C.and 20% RH. After 24, 48 and 72 hours the amount of unabsorbed serum wasremoved, weighed (W_(t)), and then added back into the cup. The cup plussample was then returned to the incubator until the next samplingtimepoint. The absorbency was calculated using the following formula andthe results reported in grams as an average of three replications:Calf Bovine Serum Absorbency (g)=12 g−W _(t)Peel Force Method

The peel force method was used to measure the force required to remove awound-facing layer of an adhesive dressing sample from its core layer. A2.54-cm wide double-coated adhesive tape (3M Brand Double Stick Tape, 3MCompany, St. Paul, Minn.) was adhered to the full circumference of arotatable metal wheel that was mounted on the lower jaw of an Instronmachine (Model No. 1122; Instron Corp., Canton, Mass.). A 2.54-cm widepolyester silicone adhesive tape (No. 8402 tape, 3M Company) was adheredto the double-coated tape, adhesive side out. An adhesive dressingsample (2.54 cm×10.2 cm) was placed on the silicone tape with the corelayer facing against the wheel and the wound-facing layer facing theoperator. One end of the wound-facing layer was lifted away from thecore layer to form a tab that was clamped onto the upper jaw of theInstron machine. The wound-facing layer was then peeled off of the corelayer at a 90-degree angle and at a crosshead speed of 300 mm/min. Thepeel force was recorded in grams force per 2.54-cm width as an averageof three replications.

Saline Extract Acidity Method

An adhesive dressing sample (5-cm square) was placed in a glass jarcontaining 50 ml of 0.9% sodium chloride solution. After 24 hours atroom temperature, the pH of the solution was measured.

Example 1 Multi-Layer Absorbent Wound Dressing

A multi-layer absorbent wound dressing having a backing layer, a firstabsorbent layer, a second absorbent layer, and a wound-facing layer wasprepared by the following procedure.

The first absorbent layer precursor composition (Composition A) wasprepared as follows. Acrylic acid (528 g, BASF, Mt. Olive, N.J.), 50%(w/w) sodium hydroxide solution (99 g, J. T. Baker, Philipsburg, N.J.),and 2-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone (1.32 g,Ciba Specialty Chemicals Corp., Tarrytown, N.Y.) were added to a glassjar and mixed until dissolved. Methoxypolyethyleneglycol 400 acrylate(2470 g, “NK Ester-AM-90G”, Shin-Nakamura Chemical Co., Ltd., Japan) wasadded to the jar and mixed in by shaking the jar. Lauryl acrylate (198g, Aldrich Chemical Co., Milwaukee, Wis.) and alpha-methylstyrene (3.3g, Aldrich) were added and the entire composition was mixed by shakingthe jar.

The second absorbent layer precursor composition (Composition B) wasprepared as follows. Acrylic acid (239 g), 50 (w/w) sodium hydroxidesolution (41.6 g), and2-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone (1.3 g) wereadded to a glass jar and mixed until dissolved.Methoxypolyethyleneglycol 400 acrylate (1016 g) was added to the jar andmixed in by shaking the jar. While stirring the resulting solution witha propeller, 2-ethylhexyl acrylate (1951 g, BASF Corp.) was added toprovide the finished composition.

Compositions A and B were thickened separately to between 1000 and 2000centipose by short exposure to UV light and an additional 3.25 g of2-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone was added andmixed into each composition. The thickened Composition B wasknife-coated at a thickness of 3 mil (0.076 mm) onto a conventionalpolyester release liner, followed immediately by knife-coating of thethickened Composition A at a thickness of 25 mil (.635 mm) onto theComposition B layer. A conventional polyester release liner was providedon top of the Composition A layer. The coated layers were then curedunder UV lamps (350BL, Sylvania Corp., Danvers, Mass.) at a peakwavelength of 350 nm and an intensity of 7.3 mW/cm² and a dose of 2360mJ/cm² through the top release liner to make the finished core laminateof the adhesive wound dressing. Additionally, the thickened CompositionB was separately knife-coated at a thickness of 25 mil (0.635 mm) onto aconventional polyester release liner for later testing.

A wound-facing layer was prepared by perforating a TEGADERM™ dressing(3M Company) by ultrasonic means so that the dressing contained 40holes/cm² with each hole having a diameter of approximately 15 mils(0.38 mm). The Percent Void Area was calculated to be 4.5%.

The release liner was removed from the Composition A layer (firstabsorbent layer) side of the core laminate and to this side waslaminated by hand to the adhesive side of a TEGADERM™ dressing (backinglayer). The release liner was then removed from the Composition B layer(second absorbent layer) side of the core laminate and to this side waslaminated by hand to the non-adhesive side of the wound-facing layer.The resulting completed multi-layer absorbent wound dressing materialwas cut into 10-cm×15-cm samples for test evaluations. Samples were alsosubsequently packaged and sterilized by irradiating at approximately 30kGy.

Example 2 Multi-Layer Absorbent Wound Dressing

A multi-layer absorbent wound dressing was prepared as described inExample 1, except that N-vinyl acetamide was substituted for the acrylicacid/sodium hydroxide components in the first absorbent layer precursorcomposition (Composition A) and this composition was prepared asfollows.

N-Vinyl acetamide (600 g, Showa Denko, Japan),2-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone (1.2 g), andmethoxypolyethyleneglycol 400 acrylate (2183 g) were added to a glassjar and mixed by shaking the jar until the N-vinyl acetamide wasdissolved. Lauryl acrylate (210 g) and alpha-methylstyrene (3.0 g) wereadded and the entire composition was mixed by shaking the jar.

Also, the wound-facing layer in this example contained 40 holes/cm² witheach hole having a diameter of approximately 20 mils (0.51 mm). ThePercent Void Area was calculated to be 7.8%.

The resulting completed multi-layer absorbent wound dressing materialwas cut into 10-cm×15-cm samples for test evaluations.

Example 3 Multi-Layer Absorbent Wound Dressing

A multi-layer absorbent wound dressing was prepared as described inExample 1, except that the sodium hydroxide solution component was notadded to either Composition A or Composition B. The resulting completedmulti-layer absorbent wound dressing material was cut into 10-cm×15-cmsamples for test evaluations.

Example 4 Multi-Layer Absorbent Wound Dressing

A multi-layer absorbent wound dressing was prepared as described inExample 1, except that the first absorbent layer precursor composition(Composition A) was prepared as follows.2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone (1.32 g) andmethoxypolyethyleneglycol 400 acrylate (2995 g) were added to a glassjar and mixed by shaking the jar. Alpha-methylstyrene (3.3 g) was thenadded and the entire composition was mixed by shaking the jar. Theresulting completed multi-layer absorbent wound dressing material wascut into 10-cm×15-cm samples for test evaluations.

Comparative Example 1 Absorbent Wound Dressing Without Adhesive BarrierLayer

An absorbent wound dressing was prepared as described in Example 1,except that the second absorbent layer precursor composition(Composition B) was not prepared and the final wound dressing materialdid not contain a second absorbent layer. The resulting completedabsorbent wound dressing material thus comprised a single firstabsorbent layer (Composition A layer) sandwiched between the backinglayer and the wound-facing layer. This comparative wound dressingmaterial was cut into 10-cm×15-cm samples for test evaluations.

Test Evaluations

Saline Absorbency Evaluation

Wound dressing samples from Examples 1, 2 and 4, a sample of the secondabsorbent layer from Example 1, and a commercial wound dressing sample(CLEAR-SITE™ dressing, available from ConMed Corp., Utica, N.Y.) wereevaluated for saline absorbency according to the test method describedherein. Observations were also noted of sample clarity when dry and whenwet. The results are provided in Table 1 and show that the inventionwound dressing samples (Examples 1, 2 and 4) had high absorbency(650-680%) of saline solution over a 24-hour period and hadsignificantly higher absorbency than either the separate barrier layer(from Example 1) or the CLEAR-SITE™ wound dressing sample. All dressingsamples in this test appeared clear when wet or dry. TABLE 1 SalineAbsorbency Example Absorbency (%) Clarity (Dry) Clarity (Wet) 1 660Clear Clear Second Absorbent Layer 90 Clear Clear (from Ex. 1) 2 650Clear Clear CLEAR-SITE ™ 260 Clear Clear 4 680 Clear ClearCalf Bovine Serum (CBS) Absorbency Evaluation

Wound dressing samples from Examples 1 and 4, Comparative Example 1(CE-1), and four commercial wound dressing samples (CLEAR-SITE™dressing; TEGASORB™ dressing, available from 3M Company; COMFEEL™dressing, available from Coloplast, Ltd., UK; and DUODERM™ dressing,available from ConvaTech, Montreal, Canada) were evaluated for calfbovine serum absorbency according to the test method described herein.Observations were also noted of sample residue that was present in thetest cell. The results are provided in Table 2 and show that theinvention wound dressing samples (Examples 1 and 4) had an increasinglevel of CBS absorbency between 24 and 72 hours, had a high level ofabsorbency (10 to 12 g) at 72 hours, and left no dressing sample residuein the test cell. In contrast, Comparative Example 1 (lacking a secondabsorbent layer) reached a maximum absorbency (12 g) before 24 hours andleft sample residue in the test cell. Samples from Examples 1 and 4, andComparative Example 1 showed significantly higher absorbency than thefour commercial wound dressing samples. TABLE 2 Calf Bovine SerumAbsorbency Absorbency (g) Example 24 hours 48 hours 72 hours Test CellResidue 1 8 11 12 No CE-1 12 12 12 Yes 4 7.7 9.5 10 No TEGASORB ™ 5.27.1 8.5 Yes COMFEEL ™ 3.9 5.5 5.5 Yes CLEARSITE ™ 3.3 * — No DUODERM ™2.2 3.4 3.8 Yes*Lateral swell occurred between dressing sample and test cell; observedleaking of CBS.Peel Force Evaluation

Wound dressing samples from Example 1 and Comparative Example 1 (CE-1)were evaluated for peel force (the force required to separate thewound-facing layer from the core layer) according to the test methoddescribed herein. The results are provided in Table 3 and show that amuch greater force was required to separate the wound-facing layer fromthe absorbent core layer (having a second absorbent layer) of theinvention wound dressing (Example 1) than from the core layer (nothaving a second absorbent layer) of the comparative wound dressing(Comparative Example 1). TABLE 3 Peel Force Example Peel Force (g/2.54cm) Standard Deviation 1 303 ±8 CE-1 204 ±3Saline Extract Acidity Evaluation

Wound dressing samples from Examples 1-3 and Comparative Example 1(CE-1) were evaluated for saline extract acidity according to the testmethod described herein. The results showed that wound dressing samplesutilizing partially neutralized acrylic acid or N-vinyl acetamide in thefirst absorbent layer (Examples 1-2 and Comparative Example 1) hadslightly acidic extract (pH=6.1, 5.8, and 6.0, respectively), whereasthe wound dressing sample utilizing non-neutralized acrylic acid in thefirst absorbent layer (Example 3) had much more acidic extract (pH=3.2).

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand principles of this invention, and it should be understood that thisinvention is not to be unduly limited to the illustrative embodimentsset forth hereinabove. All publications and patents are incorporatedherein by reference to the same extent as if each individual publicationor patent was specifically and individually indicated to be incorporatedby reference.

1. A multi-layer wound dressing comprising: a first absorbent layer withan absorbency greater than 300 percent; and a second absorbent,non-disintegrating layer in contact with the first absorbent layer,wherein the wound dressing is configured to be positioned on a patient'swound such that the second absorbent layer is between the firstabsorbent layer and the wound; and wherein the first absorbent layer issubstantially insoluble in water.
 2. The multi-layer wound dressing ofclaim 1, wherein the first absorbent layer comprises a reaction productof a hydrophilic, ethylenically unsaturated monomer; an acrylic acidester of a non-tertiary alcohol having 4 to 14 carbon atoms; and apolar, ethylenically unsaturated monomer.
 3. The multi-layer wounddressing of claim 2, wherein the first absorbent layer comprises thereaction product of about 50 to 80 parts by weight of the hydrophilic,ethylenically unsaturated monomer; about 5 to 30 parts by weight of theacrylic acid ester of a non-tertiary alcohol having from 4 to 14 carbonatoms; and about 10 to 30 parts by weight of the polar, ethylenicallyunsaturated monomer.
 4. The multi-layer wound dressing of claim 1,wherein the first absorbent layer has an absorbency at least 100 percentgreater than the absorbency of the second absorbent, non-disintegratinglayer.
 5. The multi-layer wound dressing of claim 1, wherein the secondabsorbent layer has an absorbency of at least 50 percent.
 6. Themulti-layer wound dressing of claim 1, wherein the second absorbent,non-disintegrating layer is adhesive.
 7. A body fluid absorbing materialcomprising the reaction product of: less than about 68 parts by weightof an acrylic acid ester of a non-tertiary alcohol having from 4 to 14carbon atoms; greater than about 28 parts by weight of a hydrophilic,ethylenically unsaturated monomer; and at least about 4 parts by weightof a partially neutralized ethylenically unsaturated carboxylic acidmonomer.
 8. The body fluid absorbing material of claim 7, wherein lessthan 50 percent of the carboxylic acid monomer is neutralized.
 9. Thebody fluid absorbing material of claim 7, wherein from 10 to 35 percentof the carboxylic acid monomer is neutralized.
 10. The body fluidabsorbing material of claim 7, wherein the acrylic acid ester comprisesa methacrylic acid ester.
 11. The body fluid absorbing material of claim7, wherein the hydrophilic, ethylenically unsaturated monomer comprisesmethoxy poly(ethyleneglycol) acrylate.
 12. The body fluid absorbingmaterial of claim 7, wherein the partially neutralized carboxylic acidmonomer comprises from about 4 to 30 parts by weight of the body fluidabsorbing material.
 13. The body fluid absorbing material of claim 7,wherein less than 40 mole percent of the carboxylic acid monomer isneutralized.
 14. The body fluid absorbing material of claim 7, whereinthe carboxylic acid monomer is neutralized by a base selected from thegroup consisting of sodium hydroxide, potassium hydroxide, lithiumhydroxide, ammonium hydroxide, triethylamine, sodium ethoxide, sodiummethoxide, or combinations thereof.
 15. A body fluid absorbing materialcomprising the reaction product of: less than about 68 parts by weightof an acrylic acid ester of a non-tertiary alcohol having from 4 to 14carbon atoms; greater than about 28 parts by weight of a hydrophilic,ethylenically unsaturated monomer; and at least about 4 parts by weightof N-vinyl acetamide.
 16. The body fluid absorbing material of claim 15,wherein the acrylic acid ester comprises a methacrylic acid ester. 17.The body fluid absorbing material of claim 15, wherein the hydrophilic,ethylenically unsaturated monomer comprises methoxy poly(ethyleneglycol)acrylate.